CAMSTech-2020 1OP Publishing IOP Conf. Scrics: Materials Science and Enginccring 919 (2020) 062017 doi:10.1088/1757-899X/9 19/6/062017 Methanol as the main substitute for petroleum fuels AV Fominykh Department of thermal engines, automobiles and tractors, Vyatka State Agricultural ‘Academy, 610017, Kirov, October prospect, 133, Russian Federation E-mail: aleksander.fom@yandexu Abstract. Among the known altemative fuels, alcohols, primarily methyl and ethyl, are of the greatest interest as a mass promising fuel. The prospect of using them as alternative fuels is determined mainly by the availability of raw materials. Methanol in this respect is more preferable, since the basis for its production can be natural gas, coal, shale, natural carbonates, various wastes, otc, In addition, well-established production technology and acceptable technical and economic indicators are important. Currently, methanol is obtained mainly from natural gas, and given the significant reserves of solid fuels, itis promising to obiain it from coal. Potential raw materials for expanding the production of methanol can also serve as associated and waste gases of metallurgical and Ferroalloy production, natural carbonates, and in the future, it is possible to use carbon dioxide trom the air. The article presents the main methods of methanol production, ‘Methanol is one of the most important products produced by the chemical industry in terms of value and scale of production, which is due to the variety of its applications: the production of acetic acid, synthetic protein preparations, use as a motor and energy fuel, etc. Unlike widely used natural gas, methanol is a liquid under normal conditions, and its distribution and storage system on Board the vehicle is simpler. In addition, methanol has a higher energy density compared to natural gas. Compared with potroloum fuels, mothanol has a largo latent heat of vaporization, lowor hoat of combustion, high anti-knock properties, wider ignition limits, and better energy performance. ‘Theoretically, the required emount of air for the combustion of 1 kg of methanol is half as much as for gasoline. This is due to the presence of bound oxygen in the methanol molecule, which helps to reduce the heat of combustion. For stoichiometric combustion, approximately double the mass amount of methanol must be supplied to the engine, and therefore certain changes must be made in the power system (to increase the flow sections of the fuel jets and the performance of the fuel pump). To ensure sufficient power reserve, the volume of the fuel tank must be approximately doubled, which is considered one of the disadvantages of methanol. At the same time, the heat of combustion of fuel-air mixtures of mothanol and gasoline is almost tho samo, so that when switching to methanol (other things being equal), the engine power does not decrease. However, due to the high heat of vaporization and less air required for combustion, the evaporation of methanol in the intake system causes a significant decrease in temperature, which increases the charge density of the cylinder and leads to an increase in the power and effective efficiency of the engine [1-6]. Due to the low pressure of saturated methanol vapors, itis difficult to staré the engine cold and warm up. Cutting out the heat of methanol vaporization reduces the temperature of the fuel-air mixture in the inlet pipe during evaporation by more than 100 K, which makes it difficult to obtain a homogeneous Cent frm this werk maybe used una the toms ofthe Cres Commons Atibuten 3.0 ence Any uthrdsbution Pabished onde license by ToP Pabishing Ld 1CAMSTech-2020 IOP Publishing IOP Conf. Series: Materials Science and Engineering 919 (2020) 062017 doi:10.1088/1757-899X/919/6/062017 mixture and its uniform distribution across the cylinders (with a standard ice intake system with electric ignition). ‘Wider ignition limits for methanol-air mixtures allow the engine to operate with poor compositions of mixtures, which improves the indicator efficiency, reduces fuel consumption at partial loads, makes it easier to adjust the engine for the composition of the mixture under operating conditions and reduces the toxicity of exhaust gases. Important advantages of methanol include its high anti-knock resistance, which makes it possible to increase the compression ratio to 32-14 units. High anti-knock properties of methanol allow us to consideritas a high-octane additive to petroleum gasoline, which makes it possible to exclude the use of highly toxic lead anti-detonators Since methanol is 2 liquid hydride and contains 12.5% hydrogen by mass, it can be used on Board a car to store hydrogen with subsecuont conversion to hydrogen-containing gas fuel. In addition, synthotic gasoline can be obtained from methanol [7-13]. Almost all known methods for producing methanol are based on the interaction of carbon and hydrogen oxides at elevated temperatures and pressures in the presence of a catalyst. In industry, the production of methanol has much in common with the production of ammonia, acetylene, higher alcohols, hydrocarbons, etc. In general, the technological process involves the production of the initial gas and the subsequent synthesis of methanol from it as a chemical product witha high degree of pusty. For the use of methanol as a fuel, a high degree of purification is not necessary, and such impurities as hydrocarbons, higher alcohols, and dimethyl ether only improve its energy performance. As a fuel, you can successfully uso methanol-raw, containing up to 20% water by waight, the cost of which is ch lower duo to the exclusion of the process of rectification [14-19] ‘The synthesis of methanol from carbon and hydrogen oxides proceeds by the following main Teactions: CO+2H, > CH.OH, C0, +3H, > CH,OH +H,0 According to stoichiometric coefficients the ratio Hs COin the source gas must be equal to 2, and the tatio He:CO> - 3. Reactions are reversible, direc: reactions occur with the release of heat. In addition to those the ondothermic reversible roaction occws during the cynthesis of methanol CO, +H, CO+H,O w Based on the research performed, the mechanism of methanol synthesis is proposed. Its essence is that on oxide catalysts, methanol is formed from carbon dioxide, which is prosont in tho initial mixture or is formed by a reversible reaction (1). Tho synthesis scheme can be ropresentad as follows: CO<+2-_> co, +CH OH + H,0 ‘Thermodynamic calculations show that at atmospheric pressure, only 2% of methanol can be obtained from the source gas, but its yield increases significantly with increasing pressure and can teach 100%. OF course, thatthe yields of methanol in the production differ from the calculation. During synthesis, along with the above main reactions, a number of side effects occur: CO, +3H, CH, +H,0, CO, +4H, OCH, +2H,0, nCO+(2n+1)H, OC,H,,., +nH,0, Q) nCO+ MH, C,H, OH +(n-1)H,0, @) 2CO+4H , + (CH,),0 +H,0, @) 2€0 + C+CO (3) It is possible to divide the formation of by-products by selecting highly effective and selective catalysts, but it is impossible to completely eliminate these reactions, especially (5). There is aCAMSTech-2020 IOP Publishing 1OP Conf. Series: Materials Science and Engineering 919 (2020) 062017 doi:10.1088/1757-899X/919/6/062017 catburization of catalysts, which makes it necessary to periodically regenerate or replace them. The use of methanol as 2 fuel is associated with the need for the prasence of such components as hydrocarbons (2), higher alcohols (3), dimethyl other (4), which must be provided by the technology of its production. It is known that the source gas for the synthesis of methanol must contain components in aratio close to stoichiometric. It can be obtained from any type of raw material containing a hydrocarbon or carbon, but to ensure stoichiometry in most cases, the composition of the gas must be adjusted. ‘The main raw material for producing the initial gas is natural gas. In the process of preparing it for the synthesis of methanol, oxygen vapor, steam, sieam with CO: dosing, high-iemperature and some other types of conversion or a combination of them are used [20-27]. Steam conversion of natural gas in tube furnaces at atmospheric pressure is usually performed by dosing carbon dioxide. The process of high-temperature conversion of methane can be carried out at any pressure, since the high temperature ensures a low content of methane inthe converted gas. This process provides the same pressure both at the gas preparation stage and at the methanol synthesis stage. Gasification of liquid heavy oil residues is carried out on a catalyst at atmospheric or elevated pressure by reaction 3C,Fyzp +0.5nEhO +1,250, >3CO+2.750H, « Gasification of coal and shale is a high-temperature process of interaction of fuel with oxidants (oxygen, water vapor, carbon dioxide, etc.), carried out in order to produce flammable gases. Inthis way, you can get a gas of any given composition, determined by temperature, pressure, and the composition of the oxidizer used. Gasification is caried out in @ fluidized bed of the catalyst at a pressure of up to 4 MPa at temperatures of 1250-1700 K. For tho first time, methanol was obtained in the 17th contury by dry distillation of wood, which was the main method for a long time. After the development of the process for producing a mixture of H:, CO, and CO> gases, industrial production began. Until the 70-1es of the last century, almost completely methanol was used as a chemical raw material. Then the scope of its applicetion hes significantly expanded, and primarily due to its use as an alternative fuel In industrial conditions, methanol is prochiced on zinc-chromium oxide catalysts at a temperature of 630-650 K, a pressure of up to 40 MPa and a high volume velocity of the circulating gas. As the temperature increases, the activity of the zinc-chromium catalyst increases, but up to a certain limit. In recent years, copper-zinc-chromiun catalysis applied to aluminum oxide and reduced at 410-450 K Thoy havo high activity at 470-570 K and different prossures [28-36]. ‘When synthesized on catalysts, in addition to methanol, « large amount of impurities is formed. These are simple and complex esters, aldehydes, ketones, formels, acetals, higher alcohols, hydrocarbons, etc. However, their content in most cases is insignificant and the total amount does not exceed 5% by weight. ‘The main by-product formed during the synthesis of methanol is water. Its content ranges from 6-20% by weight. The content and composition of micro-mixtures and water in different inclstries depends on the quality of raw materials and their preparation, on the content of carbon dioxide in the gas, and the technological mode of synthesis. The main process for removing impucities is rectification, The process of obtaining methanol from carbon and hydrogen oxides includes a number of stages that are mandatory for any technological scheme of synthesis, differing mainly in hardware design. The most interesting aro the schemes for the synthosis of mothanol of high unit power. Whero liquid hydrocarbon raw matorials after catalytic or absorption purification from sulfur impuritios are mixed with water vapor at 1070-1120 K. The conversion of raw materials into the source gas is carried out in the presence of a Nickel catalyst. The heat of the waste gases is used to produce process steam. After cooling, the resulting gas is compressed to 5-10 MPa and sent to the synthesis reactor. Synthesis is carried out over a copper-containing catalyst at a temperature of 470-570 K and apressure of 5-10 MPa. ‘The service life ofthe catalyst is 3-4 years. The reaction mixture is cooled by a cold source gas at several points along the height of the actor. The gases leaving the reactor pass through a series of heat exchangers and enter the separator. The condensed crude methanol is subjected to rapid evaporation andCAMS Tech-2020 IOP Publishin, JOP Conf, Series: Matcrials Science and Engineering 919 (2020) 062017 doi: 10. 1088/1757-899X/9 19/6(062017 sent for rectification. ‘The process is characterized by high efficiency of heat recovery, The technological scheme of the methanol production process is known, which allows to slightly reduce the specific consumpiion of methane per 1 ton of methanol. According to this scheme, the first steam conversion reactor converts approximately half of the initial mass of methane. The other helf is mixed with gases coming out of the first steam conversion reactor and enters the second (autothermic) stoam oxygen conversion reactor, where methane is converted in the presence of oxygen and at high temperatures. The resulting source gas is compressed to the required pressure and fed to the methanol synthesis unit, from where the raw methanol enters the rectification and purification unit. The oxygen required for conducting steam-oxygen conversion reactions in auto-thermal conditions are obtained from the air separation unit [37-45] When using methanol as a high-octane additive to gasoline, it is necessary to introduce special additives that prevent stratification of mixtures of higher alcohols C: — C,, Therefore, the process of Joint production of methanol and these alcohols is of great interest Tho process of obtaining methanol and alcohols C: — C; includes the following stages: purification of natural gas from sulfur compounds; conversion of natural gas with steam and carbon dioxide in tube furnaces under pressure; purification of converted gas from excess carbon dioxide: joint synthesis of methanol and alcohols; rectification of raw methanol with the preperation of an alcohol mixture of a given composition. The source gas obtained in tubular fumaces and compressed passes through a carbon filter, where it is purified from iron carbonyls and mixed with the circulating gas. The resulting gas mixture is heated hy heat exchange with the gas coming out of the reactor. In the reactor, the process takes place on 2 modified catalyst; the temperature in the catalysis zone is adjusted automatically by introducing cold gas betwoon the layers of the catalyst. Tho reaction mixture from the catalysis zone with a temperature of 630-650 K enters the heat exchanger, whar it is cooled to 520 K and thon to thonoxt heat exchanger. Then the gas pesses through a remote heat exchanger, where it is cooled to 380 K while partially condensing vapors of methanol, alcohols C2~ C: and water. The final cooling of the gas to 300...310 K and condensation take place in the air cooling unit. The condensate is separated from the unreacted gas in the separator and goes to the collector, and then to the warehouse and rectification, Problems related to the economy of natural hydrocarbon raw materials (oil and natural gas) led to the development of a process for the synthesis of methanol on a new basis - from coal. A huge number of enterprises in the world use it as a raw material. Large capital investments are offset by low raw material costs. The thermal efficiency of the methanol synthesis process from coal is 58%, from natural gas - 66% [46-54]. Gas emissions from metallurgical and other industries rich in H:, CO, COz, in particular ferroalloy, are of particular interest as raw materials for producing methanol. Using them, you can get both fuel methanol and hycrocarbon fuel, but the former is more profitable in terms of efficiency. Natural catbonates can serve as a potential raw material for producing methanol, and in the future, carbon dioxide from the air. Hydrogen for these processes can be obtained by pyrolysis from water, References [1] Sendilvelan $ and Bhaskar K 2016 Russian Journal of Chamistry 9(4) 692-6 [2] LiH-B, Wang W-H, Qian X et al. 2016 Catalysis Science and Technology 6(11) 3971-5 [3] Anfilatov A A and Chuvashev A N 2020 IOP Conf. Series: Materials Science and Engineering 862 062069 [4] Likhanov VA and Lopatin © P 2020 IOP Conf. Series: Materials Science and Engineering 862 062014 [5] Anfilatov A A and Chuvashev A N 2020 IOP Conf. Series: Materials Science and Enginesring 862 032052 [6] Lozhkina O V and Lozhkin V N 2016 Transportation Research Part D: Transport and Environment 47 251-64 [7]__Likhanov VA, Lopatin 0 P and Vylegzhanin PN 2020 JOP Conf, Series: Materials Science and